Aryl-ether-sulphone monomers and aryl-ether-keytone-sulfphone polymers

ABSTRACT

Benzofuran-ether-sulphone monomers of formula ##STR1## and ether ketone polymers derived therefrom of formula ##STR2##

This invention relates to novel aryl-ether-sulphone monomers and topolymers and copolymers, preferably aryl-ether-ketone-sulphone (AEKS)polymers and copolymers, containing units derived from these monomers.

Monomers for making AEKS polymers are often difficult and expensive toproduce. One aspect of the present invention provides a monomer whichcan be made from readily available starting materials by a simpleone-step process.

The aspect accordingly provides a compound of formula ##STR3## whereineach R independently is H, or C₁ -C₁₀ alkyl, and each R' independentlyis H. C₁ -C₁₀ alkyl, or Cl or F, having at least one reactive hydrogenon each of the two end benzo-rings. Preferably, all the R groups will beH. Also preferably, the ether --O-- groups will be in the para-positionrelative to the sulphone group and to the. furan oxygen. The mostpreferred monomer thus has the formula ##STR4##

These aryl furan-ether-sulphone-ether-furan (FESEF) monomers may beprepared, for example by a method comprising reacting a dibenzofurancompound of formula ##STR5## wherein M is an alkali metal, preferablyNa, with a dihalide compound formula ##STR6## wherein X is halogen,preferably Cl, the molar ratio of the reacted dibenzofuran compound tothe reacted dihalide compound being 2:1.

Appropriate starting materials, such as 2-hydroxydibenzofuran and4,4'-dichlorodiphenylsulphone, are readily available in appropriatelypure grades, and may for example be simply reacted by known proceduresin the presence of alkali metal hydroxide (preferably sodium hydroxide)which produces the salt fore of the dibenzofuran for the above reaction.

The novel FESEF monomers may be used to produce polymers for examplehaving a repeat unit of formula ##STR7## wherein R and R' are as definedabove, and Ar is a mono- or poly-nuclear aromatic moiety in which two ormore arylene groups if present may be linked by --CO--, --O--, --C(CH₃)₂--, --C(CF₃)₂ --, or by a direct or fused-ring bond. Again it ispreferred that all the groups are H and that the ether --O-- groups arein the para positions, the most preferred polymers thus having therepeat unit ##STR8##

These FESEFKetone polymer units may be made by condensing a FESEFmonomer as hereinbefore defined with a diacid halide, for exampleterephthaloyl chloride or isophthaloyl chloride, so that the FESEFKetoneunit is the product of condensing a compound of formula ##STR9## with adiacid halide compound of formula

    X--CO--Ar--CO--X

in the presence of a Lewis acid, preferably also in the presence of aLewis base controlling agent for the Lewis acid.

The invention includes random or block copolymers of such FESEFKetonerepeat units together with aryletherketone repeat units, preferablypresent in the form of a polymer pre-block, for example as described inour copending British Patent Application (RK419), the disclosure ofwhich is incorporated herein by reference. Preferably, the copolymerswill comprise 30 to 60 mol % of the aryletherketone repeat units,although higher and lower proportions thereof are not excluded. Suitablearyletherketone repeat units are described, for example in our publishedInternational Application WO90/00573, the disclosure of which isincorporated herein by reference.

The invention also provides a method of making the FESEFKetone polymershereinbefore described comprising

(A) reacting a compound of formula ##STR10## or a monomer, oligomer orpolymer pre-block having two terminal moieties of formula (TT) ##STR11##wherein each R independently is H, or C₁ -C₁₀ alkyl, and each R'independently is H, C₁ -C₁₀ alkyl, or Cl or F, having at least onereactive hydrogen on each of the two end benzo-rings, with a diacidhalide component of formula

    X--CO--Ar--CO--X

or

(B) self-reacting a monomer, oligomer, or polymer pre-block having oneterminal moiety (TT) as above and one terminal acid halide group --COX,in the presence of a Lewis acid, preferably also in the presence of aLewis base controlling agent for the Lewis acid.

Polymers could alternatively be made from acid halide-terminatedderivatives of the compound (A) or terminal moieties (TT) with anarylene moiety having two active terminal hydrogens.

These preferred methods may be carried out according to the modifiedFriedel Crafts procedures generally described in our EP-A-0124276, usinga catalytic molar excess of Lewis acid over the total Lewis basecontrolling agent and Lewis basic groups in the monomers; or accordingto an alternative procedure described in our copending British PatentApplication 9010175.9 using a weak Lewis base as controlling agent in amolar amount which equals or exceeds the mount of Lewis acid, the latterbeing used in a molar amount which exceeds the amount of strongly Lewisbasic species present. The disclosures of both of these references areincorporated herein by reference.

The following Example illustrates the use of a FESEF monomer, preparedby the aforementioned reaction from 2-hydroxydibenzofuran and4,4'-dichlorodiphenylsulphone to form a block copolymer as described anddefined in our copending British Patent Application (RK419), thedisclosure of which is incorporated herein by reference.

The materials used were AlCl₃ as Lewis acid, dimethyl sulphone (DMS) asLewis base, terephthaloyl chloride (TPC) 4,4'-diphenoxybenzophenone(DPB), the FESEF monomer, and 4-phenoxybenzophenone as end capper, inthe following amounts, with dichloromethane as diluent:

    ______________________________________                                                Reactant     mol     mass (g)                                         ______________________________________                                        EK        AlCl.sub.3     0.30550 40.7354                                      BLOCK     DMS (Lewis base)                                                                             0.08458 7.9618                                                 TPC (1st addition)                                                                           0.02666 5.4133                                                 DPB            0.03333 12.2140                                      EKS       TPC (2nd addition)                                                                           0.02973 6.0348                                       BLOCK     FESEF monomer  0.02222 12.9454                                                End Capper     0.00167 0.4572                                       ______________________________________                                    

Diluent=dichloromethane of which 50 ml was added at the start, with afurther 20 ml used to wash m the reactants.

A reaction vessel fitted with a PTFE stirrer, thermocouple, and nitrogeninlet containing the required amount of dichloromethane diluent waspre-cooled to minus 13° C., and the required amount of aluminum chloridecatalyst was added while stirring, keeping the temperature below -5° C.,followed by the required amount of dimethylsulphone (Lewis base), whichwas added slowly, not allowing the temperature to rise above minus 5° C.The required molar quantity of DPB (previously referred to) was thenadded together with just enough TPC (previously referred to) to producethe EK block. The nitrogen was then turned off and a scrubber attachedwhilst the temperature was allowed slowly to reach 20° C. After 3/4 ofan hour the scrubber was replaced by the nitrogen inlet and the reactionvessel was cooled to below 0° C. The FESEF sulphone monomer was added inthe required molar quantity together with sufficient additional TPC toform the copolymer and together with an appropriate amount of an endcapper, 4-phenoxybenzophenone, as known per se. The temperature was thenraised slowly to 20° C. and the copolymer gelled as the reactionprogressed to completion over a period of about 5 hours. The copolymergel was decomplexed by vigorous blending in iced water until white,after which it was filtered and washed in known manner. After stirringfor more than 6 hours in distilled water, followed by boiling for 30minutes, the polymer fluff produced was filtered and washed 3 times withdistilled water followed by drying overnight at 125° C. The resultingblock copolymer has glass transition temperature Tg (DSC)=194° C.,fastest crystallization temperature Tc (DSC)=252° C., and meltingtemperature Tm (DSC)=363° C., measured by the well known method of DSC(Differential Scanning Calorimetry).

EXAMPLE 2

Preparation of ##STR12## 40 g (1 mol) of NaOH dissolved in 100 mls ofdistilled water was added to a 2 liter reaction vessel fitted with amechanical stirrer, nitrogen inlet/outlet. Dean-Stark head andcondenser. To the aqueous solution was then added to 1 liter ofN-methyl-2-pyrolidinone (N.M.P.), 100 mls of toluene and 184 g (1 mol)2-hydroxydibenzofuran. The reaction mixture was heated to boiling andthe water removed by use of the Dean-Stark head. When all the water hadbeen removed the reaction mixture was allowed to cool slightly, under astream of dry nitrogen, 115 g (0.4 mol) of 4,4'-dichlorodiphenylsulphonewas added to the anhydrous sodium salt of 2-hydroxydibenzofuran in theN.M.P. The reaction mixture was then heated to 200° C. for 4 hours.After this time the mixture was allowed to cool to room temperature. Thecrude product was precipitated by pouring the reaction mixture into 3liters of methanol. The crude solid was filtered and re-slurried indeionised water in order to remove sodium chloride. After filtering, thecrude product was again slurried in 2 liters of methanol and thenfiltered in order to remove the excess 2-hydroxydibenzofuran. Afterfiltering, the crude solid was dissolved in 1 liter of chloroform anddecolourised with charcoal (10 g). After removing the chloroform theproduct was crystallised from a mixture of methanol: 1.2-dichloromethane(1:1), giving a white crystalline product having a melting point of161°-162° C. The purity as measured by DSC was found to be 99.23%. Theyield was 70%, 163 g.

EXAMPLE 3

Preparation of the Homopolymer ##STR13##

To a 150 ml reaction flask fitted with a mechanical stirrer and nitrogeninlet/outlet was added 30 mls of anhydrous dichloromethane. Aftercooling the flask to -20° C., 10 g (0.075 mol) of anhydrous aluminiumchloride was added. Having allowed the slurry to cool back to -20° C.1.61 g (0.017 mol) of dimethylsulphone was added to the slurry keepingthe temperature of the slurry below -10° C. Also at -20° C. 5 g(8.58×10⁻³ mol) of the dibenzofuran sulphone monomer from Example 2 wasadded to the reaction flask along with 1.74 g (8.58×10⁻³ mol) ifterephthaloyl chloride, Last traces of these last two components werewashed into the reaction vessel with a further 20 mls of anhydrousdichloromethane. The reaction was then allowed to warm, whilst stirring,to 20° C. During this time hydrogen chloride was evolved and slowly thereaction mixture thickened and eventually set. After 5 hours at 20° C.the polymer was decomplexed from the aluminium chloride by blending in awaring blender in iced water. The white polymer fluff was filtered offand slurred in deionised water at room temperature for 6 hours. Afterthis time the slurry was heated to boiling for 1 hour after which thepolymer fluff was filtered off and washed on the filter with 3×100 mlsof deionised water. The polymer fluff was dried at 125° C. overnight.

The I.V. of the polymer was 1.54 dl/g measured as a 0.1% solution insulphuric acid. The Tg of the polymer was 260° C.

EXAMPLE 4

Following the procedure outlined in Example 3 a random copolymer wasprepared using the following reagents.

    ______________________________________                                        FESEF          2.2241  g      3.8175 × 10.sup.-3                                                                mols                                  4,4'-diphenoxybenzo-                                                                         3.2639  g      8.9075 × 10.sup.-3                                                                mols                                  phenone                                                                       4-phenoxybenzophenone                                                                        0.1969  g      7.6308 × 10.sup.-4                                                                mols                                  terephthaloyl chloride                                                                       2.6609  g      1.3108 × 10.sup.-2                                                                mols                                  dimethyl sulphone                                                                            2.162   g      2.3 × 10.sup.-2                                                                   mols                                  aluminium trichloride                                                                        11.25   g      8.437 × 10.sup.-2                                                                 mols                                  dichloromethane                                                                              75      mls                                                    ______________________________________                                    

The I.V. of the resultant random copolymer was 0.73 dl/g.

The Tg of the random copolymer was at 193° C., as measured by DSC, andTm of 348° C.

EXAMPLE 5

Following the procedure outlined in Example 3 a random copolymer wasprepared using the following reagents.

    ______________________________________                                        FESEF          3       g      5.1493 × 10.sup.-3                                                                mols                                  4,4'-diphenoxybenzo-                                                                         4.3963  g      0.01199   mols                                  phenone                                                                       terephthaloyl chloride                                                                       3.4812  g      0.01714   mols                                  dimethyl sulphone                                                                            3.2     g      0.034     mols                                  aluminium trichloride                                                                        16.5    g      0.1237    mols                                  dichloromethane                                                                              100     mls                                                    ______________________________________                                    

The I.V. of the resultant random copolymer was 1.94 dl/g.

The Tg of the random copolymer was 200° C.

I claim:
 1. A polymer having a FESEFKetone repeat unit of formula ##STR14## wherein each R independently is H, or C₁ -C₁₀ alkyl, and each R' independently is H, C₁ -C₁₀ alkyl, or Cl or F, and Ar is a mono- or poly-nuclear aromatic moiety in which two or more arylene groups if present may be linked by --CO--, --O--, --C(CH₃)₂ --, --C(CF₃)₂ --, or by a direct or fused-ring bond.
 2. A polymer according to claim 1, wherein the FESEFKetone unit is the product of condensing a compound of formula ##STR15## with a dihalide compound of the formula

    X--CO--Ar--CO--X

in the presence of a Lewis acid.
 3. A random or block copolymer comprising FESEFKetone repeat units as defined in claim 1 together with aryletherketone repeat units.
 4. A block copolymer according to claim 3 wherein at least the aryletherketone repeat units are present in the form of a polymer pre-block.
 5. A copolymer according to claim 3 comprising 30 to 60 mol % of the aryletherketone repeat units.
 6. A polymer according to claim 3, having a repeat unit of the formula ##STR16##
 7. A polymer according to claim 5, which is a random copolymer. 